Fe-Ni-P-RE multicomponent alloy plating layer, and electrodeposition preparation method and application thereof

ABSTRACT

An Fe—Ni—P-RE multicomponent alloy plating layer, electrodeposition preparation method, and plating application. The alloy plating layer obtained via electrodeposition contains elements Fe, Ni, P and RE, with the following mass percentages Fe— 16%-65%, Ni— 25%-70%, combined Fe and Ni— 63%-91%, RE 1.6%-25%, and the balance being P. The plating solution mainly contains the following components: ferrous salt, nickel salt, NaH 2 PO 2 , RECl 3 , H 3 BO 3  and Na 3 C 6 H 5 O 7 . A multicomponent alloy plating layer of different components can be obtained by adjusting the main salt and complexing agent in the plating solution and by adjusting the process Enabled is controllable adjustment to the components of the obtained plating layer while saving costs, improved characteristics such as the thermal expansion coefficient, electrical property, magnetic property, etc., and products and methods very suitable for applications in the field of micro-electronics.

TECHNICAL FIELD

The present invention relates to the field of electroplating,specifically to a Fe—Ni—P-RE multicomponent alloy plating layer and theelectrodeposition method and application thereof. The prepared alloyplating layer is suitable for applications in fields such asmicroelectronics and semiconductor function devices.

BACKGROUND OF THE INVENTION

Fe—Ni alloys represented by Invar alloy, Kovar alloy and perm-alloy, arewidely accepted for their advantages of the performance in thermalexpansion and soft magnetic properties. In recent years, following thedevelopment of technologies in the microelectronics industry, theadvantages of Fe—Ni alloy materials in nature such as lead-freesolder-ability and interface reaction rate are gradually beingrecognized by researchers and investigated in depth. The relatedachievements are being published continuously from the studies. A largeamount of study data shows that Fe—Ni thin film materials hold goodsolder-ability and slow interface reaction rate. It lays the foundationfor the wide application of Fe—Ni thin film materials in themicro-electronics industry. Nevertheless, if used as magnetic core ofinductor devices in chips, the existing Fe—Ni thin film materials tendto consume energy in their high-frequency application, which results ina rapid decrease of inductance and lost advantages in power conversion.Therefore, more research is urged to carry out further studies in orderto improve the performance of materials.

Compared with the preparation methods such as magnetron sputtering,chemical vapor deposition (CVD) and atom layer deposition frequentlyused in the microelectronics industry, the electroplating method ispreferred in the industries due to its advantages of low upfrontinvestment on equipment, easy and feasible operation, short cycle ofmaterial preparation, high efficiency, low operation cost, etc.

SUMMARY OF THE INVENTION

In view of the shortcomings of existing technologies, the presentinvention aims to provide a Fe—Ni—P-RE multicomponent alloy platinglayer as well as the electrodeposition method and application thereof.

Through adding appropriate additives and adjusting the processparameters, an alloy plating layer with controllable composition isobtained through electroplating.

In order to realize the purposes above, the technical scheme of thepresent invention is:

A Fe—Ni—P-RE multicomponent alloy plating layer that is plated on asubstrate by means of electroplating comprises the elements of Fe, Ni, Pand RE, wherein the mass percentages of various elements arerespectively: Fe being 20˜65%, Ni being 25˜70%, Fe+Ni being 65˜90%, REbeing 2˜25%, the balance being P; and RE being rare earth element.

Said rare earth element is one or two selected from La, Ce, Pr, Nd, Eu,Gd and Tb.

Said substrate is copper or other metal material.

An electrodeposition preparation method of said Fe—Ni—P-REmulticomponent alloy plating layer that the alloy layer is electricallydeposited on substrate at constant voltage or constant current, wherein:the used plating solution comprises main salt(s), complexing agent(s)and water, the chemical composition and concentration of said mainsalt(s) are: ferrite being 0.01-0.09 mol/L, nickel salt(s) being0.01-0.09 mol/L, NaH₂PO₂ being 0.1 mol/L, RECl₃ being 0.5-4 g/L, H₃BO₃being 0.5 mol/L, said complexing agent being Na₃C₆H₅O₇ with aconcentration of 0.1-0.2 mol/L in the plating solution, the balancebeing water. HCl or H₂SO₄ is used to adjust the pH value of the platingsolution to 2˜5 and the temperature of the plating solution is 45˜70° C.

The current density at constant current is 3.0˜9.0 A/dm³ and the voltageat constant voltage is −0.9˜−3.0 V.

In said plating solution, the ferrite(s) is one or two selected fromFeSO₄ and FeCl₂. The nickel salt(s) is one or two from NiSO₄ and NiCl₂.Said plating solution can also comprise an assistant complexing agent(s)to promote co-deposition of multicomponent system whose concentration is0.005-0.015 mol/L.

Said assistant complexing agent(s) can be one or two from EDTA-2Na orNH₄Cl.

Said plating solution can also comprise a brightener and a wetting agentto improve the surface quality of plating. Said brightener is saccharinsodium or butynediol with a concentration of 0.5-2.5 g/L. Said wettingagent is sodium dodecyl sulfate with a concentration of 0.1-0.5 g/L.

According to the present invention, before electrodeposition of alloyplating layer on a substrate, a copper sheet is treated on the surfaceto remove any dust, oil or grease and oxide, etc. Then 5% H₂SO₄ is usedto activate its surface. Then the substrate is washed with de-ionizedwater before placed in a plating tank to carry out electrodepositionprocess.

The ratio among different components in the plating layer can beadjusted through modifying the content(s) of the main salt(s), thecontent(s) of the complexing agent(s) in the plating solution and anyone or more process parameters during the process of electrodeposition.

The alloy plating layer according to the present invention is applied inthe fields such as microelectronics and semi-conductor function devices.

The principle of the present invention is as follows:

The magnetism of solid material comes from the spin and orbital motionof various charged particles. As for transition metals, the wavefunctions of 3d electrons overlap between each other to provide themetals such as Fe, Co, Ni, Yb, Gd and their alloys ferromagnetismthrough direct exchange interaction. As for rare earth metals, the 4felectron cloud of the adjacent atoms do not overlap with each other. Butthe s itinerant electrons can function as a medium through indirectexchange interaction to cause f electrons to change spin orientation andhence show spin magnetization: for light rare earth metals whose atomicnumber is smaller than Gd, the magnetic moment of 3d atom is parallelwith the magnetic moment of 4f atom, so the magnetic moments of themferromagnetic couple with each other; for heavy rare earth metal whoseatomic number is higher than Gd, the corresponding magnetic moments areanti-parallel showing ferri-magnetic coupling effect. If the rare earthelement(s) is added in Fe, Ni, the Slater-Pauling curve can be used toanalyze the atomic magnetic moment and the magneto-crystallineanisotropy exerted by rare earth metal. Meanwhile, with the synergisticeffect from the factors such as crystallite size, structure and materialinternal stress, the magnetism of material can also be controllable. Thepresent invention adds an appropriate amount of rare earth element(s) inthe FeNi(P) alloy to realize a controllable management on the magneticperformances of material such as coercivity, magnetization intensity andmagnetic anisotropy. Through adding P element in the plating solution,the electrical property of the plating layer is improved and hence theenergy loss at high frequency can be decreased. Through adding rareearth element(s), the performances are improved in terms of thestability of plating solution, the magnetic performance of plating layerand the corrosion resistance. The method according to the presentinvention can produce a multicomponent alloy plating layer withdifferent compositions through adjusting the formula of plating solutionand the parameters of plating process. Hence, the material indices suchas thermo expansion coefficient, resistivity, and saturation magneticinduction can be further regulated to expand the application of Fe—Nialloy materials.

The present invention has the following advantages:

1. The present invention can produce a Fe—Ni—P-RE multicomponent alloyplating layer. Through adjusting the content(s) of the main salt(s) andthe content(s) of the complexing agent(s) in the plating solution aswell as the process parameters during electrodeposition, the alloyplating layer can be produced to have different compositions so as toexpand the application of materials.

2. In the Fe—Ni—P-RE multicomponent alloy plating layer preparedaccording to the present invention, the mass percentage of Fe in theplating solution is 20%-65%, 25%-70% for Ni, 65%-90% for sum of Fe andNi. The ratio between Fe, Ni and rare earth component can be adjusted torealize the modification on thermal expansion coefficient, magneticproperty, and electrical property of film material.

3. The Fe—Ni—P-RE plating layer prepared according to the presentinvention has an improved of electric property through adding P elementin the plating solution to reduce the energy loss at high-frequencyapplication. Through adding rare earth element, the magnetic property ofplating layer is improved. Meanwhile, the surface quality is alsoimproved without adding any additive.

4. The plating solution system used in the present invention is simple,stable, low in concentration of various components, easy to extend theapplication and economically beneficial in saving cost.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the process flow chart.

FIG. 2 is the morphology picture of the sample plating layer of example1.

FIG. 3 is the X-Ray diffraction spectrum of the sample plating layer ofexample 1.

FIG. 4 is the composition analytical curve of the sample plating layerof example 1.

FIG. 5 is the morphology picture of the sample plating layer of example2.

FIG. 6 is the composition analytical curve of the sample plating layerof example 2.

FIG. 7 is the morphology picture of the sample plating layer of example3.

FIG. 8 is the composition analytical curve of the sample plating layerof example 3.

FIG. 9 is the X-Ray diffraction spectrum of the sample plating layer ofexample 4.

FIG. 10 is the composition analytical curve of the sample plating layerof example 4.

FIG. 11 is the X-Ray diffraction spectrum of the sample plating layer ofexample 6.

FIG. 12 is the morphology picture of the sample plating layer of example6.

FIG. 13 is the composition analytical curve of the sample plating layerof example 6.

FIG. 14 is the magnetic performance curve of the sample plating layer ofexample 6.

FIG. 15 is the X-Ray diffraction spectrum of the sample plating layer ofexample 7.

FIG. 16 is the morphology picture of the sample plating layer of example7.

FIG. 17 is the composition analytical curve of the sample plating layerof example 7.

FIG. 18 is the performance curve of the sample plating layer of example7.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The process flow chart of the present invention is as shown in FIG. 1and specified as follows:

The plating solution according to the present comprises main salt(s),complexing agent(s) and water.

The chemical composition and concentration of said main salt(s) are:ferrite of 0.01-0.09 mol/L, nickel salt(s) of 0.01-0.09 mol/L. NaH₂PO₂of 0.1 mol/L, RECl₃ of 0.5-4 g/L, H₃BO₃ of 0.5 mol/L; said complexingagent is Na₃C₆H₅O₇ of a concentration of 0.1-0.2 mol/L in the platingsolution, the balance being water. HCl or H₂SO₄ is used to adjust the pHvalue of the plating solution to 2˜5, and the temperature of the platingsolution is 45˜70° C.

On the basis of the basic composition as above, the plating solutionaccording to the present invention can also further comprise assistantcomplexing agent(s) (EDTA-2Na and/or NH₄Cl) to promote co-deposition ofmulticomponent system. Brightener (including but not limit to saccharinsodium, butynediol) and wetting agent (sodium dodecyl sulfate), etc.,can also be added to improve the surface quality of the plating layer.

The formulating method according to the present invention is: addingH₃BO₃ into appropriate amount of de-ionized water to dissolvecompletely, then adding Na₃C₆H₅O₇.2H₂O into the solution with agitating,and then adding the raw materials of the main salts such as FeSO₄.7H₂O,NiSO₄.6H₂O, NaH₂PO₂.H₂O and RECl₃.nH₂O in turn with agitating to mixevenly, if necessary, adding the solutions of a brightener, wettingagent and so forth, at last adding the de-ionized water to the specifiedvolume.

The electrodeposition process according to the present invention is:adjusting the pH value of the plating solution to 2-5 with HCl orH₂SO₄,then heating to 45-70° C.; meanwhile, treating the surface ofsubstrate (copper sheet or other metal material) to remove any dust, oilor grease, oxide, etc. Specifically, using 5 wt. % diluted solution ofH₂SO₄ to activate the surface and washing away the de-ionized waterbefore placing it in the plating tank; carrying out theelectrodeposition process at constant voltage or constant current.

EXAMPLE 1

Treat the surface of copper sheet substrate: remove any dust, oil orgrease, oxide; use 5% diluted solution of H₂SO₄ to activate the surfaceand wash it with the de-ionized water before placing it in the platingtank. The composition of the plating solution is: FeSO₄ of 0.039 mol/L,NiSO₄ of 0.061 mol/L, NaH₂PO₂ of 0.1 mol/L, CeCl₃ of 1 g/L, H₃BO₃ of 0.5mol/L, Na₃C₆H₅O₇ of 0.1 mol/L, the balance being water. Adjust the pHvalue of the plating solution to 2 and heat it to 57° C. Then select aconstant voltage of −1.05V and an electroplating duration of 5 min tocarry out the electrodeposition process.

The surface morphology of the plating layer is as shown in FIG. 2. TheX-Ray diffraction spectrum of the plating layer is as shown in FIG. 3.The composition analytical curve of the plating layer is as shown inFIG. 4 and the composition of the prepared plating layer is: 54.25Fe34.87Ni 9.25P1.63Ce (mass percentage).

EXAMPLE 2

Treat the surface of copper sheet substrate: remove any dust, oil orgrease, oxide; use 5% diluted solution of H₂SO₄ to activate the surfaceand wash it with the de-ionized water before placing it in the platingtank. The composition of the plating solution is: FeSO₄ of 0.020 mol/L,NiSO₄ of 0.080 mol/L, NaH₂PO₂ of 0.1 mol/L, CeCl₃ of 1 g/L, H₃BO₃ of 0.5mol/L, Na₃C₆H₅O₇ of 0.1 mol/L, the balance being water. Adjust the pHvalue of the plating solution to 2 and heat it to 55° C. Then select aconstant voltage of −1.20V and an electroplating duration of 10 min tocarry out the electrodeposition process.

The surface morphology of the plating layer is as shown in FIG. 5. Thecomposition analytical curve of the plating layer is as shown in FIG. 6and the composition of the prepared plating layer is: 38.27Fe 46.8Ni12.4P2.54Ce (mass percentage).

The thickness of the copper substrate is 250 μm, the thickness of theplating layer is 2.39 μm and the total magnetic moment in the directionparallel to the plating layer is 23.90 memu.

EXAMPLE 3

Treat the surface of copper sheet substrate: remove any dust, oil orgrease, oxide; use 5% diluted solution of H₂SO₄ to activate the surfaceand wash it with the de-ionized water before placing it in the platingtank. The composition of the plating solution is: FeSO₄ of 0.010 mol/L,NiSO₄ of 0.090 mol/L, NaH₂PO₂ of 0.1 mol/L, CeCl₃ of 1 g/L, H₃BO₃ of 0.5mol/L, Na₃C₆H₅O₇ of 0.1 mol/L, the balance being water. Adjust the pHvalue of the plating solution to 2 and heat it to 55° C. Then select aconstant voltage of −1.05V and an electroplating duration of 10 min tocarry out the electrodeposition process.

The surface morphology of the plating layer is as shown in FIG. 7. Thecomposition analytical curve of the plating layer is as shown in FIG. 8and the composition of the prepared plating layer is: 16.83Fe 65.54Ni11.56P6.07Ce (mass percentage).

EXAMPLE 4

Treat the surface of copper sheet substrate: remove any dust, oil orgrease, oxide; use 5% diluted solution of H₂SO₄ to activate the surfaceand wash it with the de-ionized water before placing it in the platingtank. The composition of the plating solution is: FeSO₄ of 0.039 mol/L,NiSO₄ of 0.061 mol/L, NaH₂PO₂ of 0.1 mol/L, LaCl₃ of 1 g/L, H₃BO₃ of 0.5mol/L, Na₃CH₅O₇ of 0.1 mol/L, the balance being water. Adjust the pHvalue of the plating solution to 2 and heat it to 55° C. Then select aconstant voltage of −1.2V and an electroplating duration of 5 min tocarry out the electrodeposition process.

The X-Ray diffraction spectrum of the plating layer is as shown in FIG.9. The composition analytical curve of the plating layer is as shown inFIG. 10 and the composition of the prepared plating layer is: 48.77Fe39.26Ni 10.16P1.80La (mass percentage).

The thickness of the sample copper substrate is 250 μm, the thickness ofthe plating layer is 4.29 μm, the surface resistance of the platinglayer is measured as 9.32*10⁻⁵Ω and the total magnetic moment in thedirection parallel to the plating layer is 98.92 memu.

EXAMPLE 5

Treat the surface of copper sheet substrate: remove any dust, oil orgrease, oxide; use 5% diluted solution of H₂SO₄ to activate the surfaceand wash it with the de-ionized water before placing it in the platingtank. The composition of the plating solution is: FeSO₄ of 0.020 mol/L.NiSO₄ of 0.080 mol/L, NaH₂PO₂ of 0.15 mol/L, CeCl₃ of 1 g/L, H₃BO₃ of0.5 mol/L, Na₃C₆H₅O₇ of 0.1 mol/L, the balance being water. Adjust thepH value of the plating solution to 2 and heat it to 55° C. Then selecta constant voltage of −1.05V and an electroplating duration of 30 min tocarry out the electrodeposition process.

The composition of the prepared plating layer is: 27.97Fe 35.73Ni13.56P22.74Ce (mass percentage).

The thickness of the sample copper substrate is 250 μm, the thickness ofthe plating layer is 2.11 μm, the surface resistance of the platinglayer is measured as 2.33*10⁻⁵Ω and the total magnetic moment in thedirection parallel to the plating layer is 19.85 memu.

EXAMPLE 6

Carry out sputter deposition of 100 nm of Ti layer and 400 nm of Culayer on a wafer and then dice it to appropriate size; treat the surfaceof the sample: remove any dust, oil or grease, oxide; use 5% dilutedsolution of H₂SO₄ to activate the surface and wash it with thede-ionized water before placing it in the plating tank. The compositionof the plating solution is: FeSO₄ of 0.039 mol/L, NiSO₄ of 0.061 mol/L,NaH₂PO₂ of 0.1 mol/L, CeCl₃ of 1 g/L, H₃BO₃ of 0.5 mol/L, Na₃C₆H₅O₇ of0.1 mol/L, the balance being water. Adjust the pH value of the platingsolution to 2 and heat it to 55° C. Then select a constant voltage of0.36 A and an electroplating duration of 30 min to carry out theelectrodeposition process.

The X-Ray diffraction spectrum of the plating layer is as shown in FIG.11. The surface morphology of the plating layer is as shown in FIG. 12.The composition analytical curve of the plating layer is as shown inFIG. 13 and the composition of the prepared plating layer is: 58.18Fe31.72Ni 6.13P3.97Ce (mass percentage). The thickness of the platinglayer is 19.9 μm and the resistivity of the plating layer is measured as3.45 Ω·μm. The hysteresis loop of the plating layer is as shown in FIG.14. The coercivity in the direction parallel to the plating layer is4.99 Oe and the magnetization intensity is 677.99 emu/cm³. Thecoercivity in the direction perpendicular to the plating layer is 28.46Oe and the magnetization intensity is 677.99 emu/cm³.

EXAMPLE 7

Carry out sputter deposition of 100 nm of Ti layer and 400 nm of Culayer on a wafer and then dice it to appropriate size; treat the surfaceof the sample: remove any dust, oil or grease, oxide; use 5% dilutedsolution of H₂SO₄ to activate the surface and wash it with thede-ionized water before placing it in the plating tank. The compositionof the plating solution is: FeSO₄ of 0.03 mol/L, NiSO₄ of 0.07 mol/L,NaH₂PO₂ of 0.1 mol/L, LaCl₃ of 1 g/L, H₃BO₃ of 0.5 mol/L, Na₃C₆H₅O₇ of0.1 mol/L, the balance being water. Adjust the pH value of the platingsolution to 2 and heat it to 55° C. Then select a constant voltage of0.36 Å and an electroplating duration of 30 min to carry out theelectrodeposition process.

The X-Ray diffraction spectrum of the plating layer is as shown in FIG.15. The surface morphology of the plating layer is as shown in FIG. 16.The composition analytical curve of the plating layer is as shown inFIG. 17 and the composition of the prepared plating layer is: 54.84Fe35.91Ni 5.14P4.11La (mass percentage). The thickness of the platinglayer is 18.3 μm and the resistivity of the plating layer is measured as6.92 Ω·μm. The hysteresis loop of the plating layer is as shown in FIG.18. The coercivity in the direction parallel to the plating layer is20.39 Oe and the magnetization intensity is 413.72 emu/cm³. Thecoercivity in the direction perpendicular to the plating layer is 38.55Oe and the magnetization intensity is 381.38 emu/cm³.

The examples described as above are the preferred implementationsaccording to the present invention. Nevertheless, the implementation ofthe present invention is not limited by any example as above. Any otherchange, modification, substitution, combination and simplificationwithout deviation from the spirit and the principle of the presentinvention shall be equivalent replacement and be included in theprotection scope of the present invention.

The invention claimed is:
 1. An electrodeposition method for an Fe—Ni—P-RE multicomponent alloy plating layer, said layer comprising the elements of Fe, Ni, P and RE; wherein: the mass percentages are, respectively: 16˜65% Fe, 25˜70% Ni, 63˜91% Fe+Ni, 1.6˜25% RE and the balance being P; RE is rare earth element, wherein said electrodeposition method comprises electrodepositing the alloy layer on a substrate at constant voltage or constant current, and with a plating solution that comprises main salts, one or more complexing agents, and water, the chemical composition and concentration of said main salts include: ferrite salt or salts of 0.01-0.09 mol/L, nickel salt or salts of 0.01-0.09 mol/L, NaH₂PO₂ of 0.1 mol/L, RECl₃ of 0.5-4 g/L, H₃BO₃ of 0.5 mol/L; said one or more complexing agents includes Na₃C₆H₅O₇ of a concentration of 0.1-0.2 mol/L in the plating solution; the balance is water.
 2. The electrodeposition method of the Fe—Ni—P-RE multicomponent alloy plating layer according to claim 1, wherein HCl or H₂SO₄ is used to adjust the pH value of the plating solution to 2˜5, and the temperature of the plating solution is 45-70° C.
 3. The electrodeposition method of the Fe—Ni—P-RE multicomponent alloy plating layer according to claim 1, wherein the current density at constant current is 3.0˜9.0 A/dm³, and the voltage at constant voltage is −0.9˜−3.0V.
 4. The electrodeposition method of the Fe—Ni—P-RE multicomponent alloy plating layer according to claim 1, wherein, in said plating solution, the ferrite salt or salts is one or two selected from FeSO₄ and FeCl₂; the nickel salt or salts is one or two selected from NiSO₄ and NiCl₂.
 5. The electrodeposition method of the Fe—Ni—P-RE multicomponent alloy plating layer according to claim 1, wherein said one or more complexing agents further comprises, in a concentration of 0.005-0.015 mol/L, one or two selected from EDTA-2Na and NH₄Cl.
 6. The electrodeposition method of the Fe—Ni—P-RE multicomponent alloy plating layer according to claim 1, wherein said plating solution further comprises a brightener that is saccharin sodium or butynediol, and the concentration of said brightener is 0.5-2.5 g/L; and a wetting agent that is sodium dodecyl sulfate of a concentration of 0.1-0.5 g/L.
 7. The electrodeposition method of the Fe—Ni—P-RE multicomponent alloy plating layer according to claim 1, further comprising treating a surface of the substrate as follows: activating the surface with 5 wt. % of diluted H₂SO₄, and then washing the surface with de-ionized water and placing the surface in a plating tank to carry out the electrodeposition method.
 8. The electrodeposition method of the Fe—Ni—P-RE multicomponent alloy plating layer according to claim 1, wherein the ratios among the components in the plating layer are adjusted by changing at least one of: (a) content of one or more of the main salts, (b) content of the one or more complexing agents in the plating solution, and (c) one or more method parameters used during the method of electrodeposition.
 9. The electrodeposition method of the Fe—Ni—P-RE multicomponent alloy plating layer according to claim 1, wherein said Fe—Ni—P-RE multicomponent alloy plating layer is electrodeposited on the substrate which is a member of a component used in a microelectronic or semiconductor device.
 10. The electrodeposition method of the Fe—Ni—P-RE multicomponent alloy plating layer according to claim 1, wherein the alloy electrodeposited in the electrodeposition method has the elements of Fe, Ni, P and RE; wherein: the mass percentages of the elements are respectively: 20˜65% Fe, 25˜70% Ni, 65˜90% Fe+Ni, 2˜25% RE and the balance being P.
 11. The electrodeposition method of the Fe—Ni—P-RE multicomponent alloy plating layer according to claim 1, wherein the electrodeposited Fe—Ni—P-RE multicomponent alloy plating layer has one or two rare earth elements selected from La, Ce, Pr, Nd, Eu, Gd and Tb.
 12. The electrodeposition method of the Fe—Ni—P-RE multicomponent alloy plating layer according to claim 11, wherein the electrodeposited Fe—Ni—P-RE multicomponent alloy plating layer has Ce or La as the rare earth element.
 13. The electrodeposition method of the Fe—Ni—P-RE multicomponent alloy plating layer according to claim 1, wherein the substrate, which the applied Fe—Ni—P-RE multicomponent alloy plating layer is applied to, is a copper substrate. 